CN114318508B - Preparation method of heavily phosphorus-doped ultralow-resistance silicon single crystal - Google Patents
Preparation method of heavily phosphorus-doped ultralow-resistance silicon single crystal Download PDFInfo
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- CN114318508B CN114318508B CN202111594443.4A CN202111594443A CN114318508B CN 114318508 B CN114318508 B CN 114318508B CN 202111594443 A CN202111594443 A CN 202111594443A CN 114318508 B CN114318508 B CN 114318508B
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- 239000013078 crystal Substances 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 13
- 239000010703 silicon Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000005204 segregation Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of a heavily phosphorus-doped ultralow-resistance silicon single crystal, which adopts the following processes in the equal-diameter working procedure: (1) In the early stage of the constant diameter, the pressure of the furnace chamber is increased from 70 to 90Torr to 180 to 220Torr; (2) In the middle of the equal diameter, the pressure of the furnace chamber is maintained to be unchanged at the high pressure which is increased to in the early period of the equal diameter; (3) In the latter stage of the equal diameter, the furnace chamber pressure is reduced to 120-150Torr from the high pressure; the crystal pulling rate is reduced at a rate of 0.01-0.2mm/hr per mm of isodiametric length throughout the isodiametric process, and the crystal pulling rate is reduced from 55-60mm/hr to 20-25mm/hr throughout the isodiametric process. The invention can overcome the phenomenon that dislocation occurs due to excessive impurity concentration in the later period of constant diameter due to segregation by controlling the pulling speed of the crystal and the furnace chamber pressure, thereby obtaining the complete single crystal without dislocation.
Description
Technical Field
The invention relates to a preparation method of a heavily phosphorus-doped ultralow-resistance silicon single crystal, and belongs to the technical field of single crystal silicon production.
Background
With the miniaturization and the improvement of the mobile performance of electronic products, strict requirements are put on the working voltage and the energy consumption of corresponding devices, and the silicon substrate materials prepared by the method are required to have extremely low resistivity. To obtain a substrate material with a low resistivity, more dopant needs to be added, which means that the preparation of a silicon single crystal is more difficult. At present, as is used As a doping agent, and the lowest resistivity can reach about 2mΩ & cm. To obtain a product having a resistivity of 1mΩ·cm or less, red phosphorus must be selected as a dopant.
The vapor pressure of phosphorus is very large, and the phosphorus is very volatile in a vacuum state, so that the doping efficiency is reduced; when the concentration of solute in the melt is high, supercooling easily occurs at the solid-liquid interface, thereby damaging dislocation-free single crystal growth; therefore, it is very difficult to obtain a silicon single crystal having a resistivity of 1mΩ·cm or less using phosphorus as a dopant.
Disclosure of Invention
The invention aims to provide a preparation method of a heavily phosphorus-doped ultralow-resistance silicon single crystal, the resistivity of the prepared silicon single crystal is less than 1mΩ & cm, and the method overcomes the phenomenon that dislocation occurs due to excessive impurity concentration in the later period of the equal diameter by improving the equal diameter process so as to obtain a complete single crystal without dislocation.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the heavily phosphorus-doped ultralow-resistance silicon single crystal comprises the following steps of:
(1) In the early stage of the constant diameter, the pressure of the furnace chamber is increased from 70 to 90Torr to 180 to 220Torr;
(2) In the middle of the equal diameter, the pressure of the furnace chamber is maintained to be unchanged at the high pressure which is increased to in the early period of the equal diameter;
(3) In the latter stage of the equal diameter, the furnace chamber pressure is reduced to 120-150Torr from the high pressure;
throughout the isodiametric process, the crystal pulling rate decreases at a rate of 0.01-0.2mm/hr per millimeter of isodiametric length.
Preferably, the crystal pulling rate is reduced from 55-60mm/hr to 20-25mm/hr throughout the isodiametric process.
In the invention, the isodiametric early stage is a stage with the isodiametric length of 0-100 mm; the mid-isodiametric period is a stage with the isodiametric length of 100-800 mm; the later stage of the equal diameter is a stage with the equal diameter length of 800-1600 mm.
Preferably, in the early stages of the isodiametric, the furnace chamber pressure is raised at a rate of 0.5-2Torr per millimeter of isodiametric length.
Preferably, at the latter end of the isodiametric period, the furnace chamber pressure is reduced at a rate of 0.05-0.1Torr per millimeter of isodiametric length.
The invention has the advantages that:
the invention can overcome the phenomenon that dislocation occurs due to excessive impurity concentration in the later period of constant diameter due to segregation by controlling the pulling speed of the crystal and the furnace chamber pressure, thereby obtaining the complete single crystal without dislocation.
Drawings
FIG. 1 is a graph showing the variation of pull rate during the isodiametric process of single crystals in example 1 and comparative examples 1 and 2.
FIG. 2 shows the furnace pressure change curves of example 1 and comparative examples 1 and 2 during the single crystal constant diameter process.
FIG. 3 shows the axial distribution of resistivity of single crystals obtained in example 1 and comparative examples 1 and 2.
Detailed Description
The invention is further described below with reference to the drawings and examples.
In the following examples and comparative examples, a single crystal of heavily phosphorus doped 8 inch silicon with a crystal orientation of <100> and a resistivity of < 1.0mΩ·cm was obtained by using a Czochralski single crystal furnace, installing a 24inch thermal field, filling 140kg of virgin polysilicon material, and performing the steps of evacuation, leak detection, melting, doping, stabilization, seeding, shouldering, shoulder turning, isodiametric ending, and the like. The following comparative analysis is performed by examples and comparative examples only on the improvement points related to the technical scheme of the present invention, and the description of other operation processes and related parameter control in the single crystal straightening process is omitted. For the omitted matters, the operations performed in the examples and comparative examples, i.e., the control of the relevant parameters, are all the same.
Comparative example 1
In the constant diameter process, the adopted process is specifically as follows:
(1) The constant diameter length is 0-100mm, the furnace pressure is rapidly increased from 90Torr to 200Torr, the pulling speed is reduced from 55mm/hr to 45mm/hr, the pulling speed is changed as shown in figure 1, and the furnace pressure is changed as shown in figure 2;
(2) The constant diameter length is 100-1600mm, the furnace pressure is kept unchanged at 200Torr, the pulling speed is reduced from 45mm/hr to 28mm/hr, the pulling speed change is shown in figure 1, and the furnace pressure change is shown in figure 2.
Comparative example 2
In the constant diameter process, the adopted process is specifically as follows:
(1) The constant diameter length is 0-100mm, the furnace pressure is rapidly increased from 90Torr to 200Torr, the pulling speed is reduced from 55mm/hr to 45mm/h, the pulling speed is changed as shown in figure 1, and the furnace pressure is changed as shown in figure 2;
(2) The equal diameter length is 100-800mm, the furnace pressure is kept unchanged at 200Torr, the pulling speed is reduced from 45mm/hr to 42mm/hr, and the crystal pulling speed reducing rate is reduced by 0-0.01mm/hr per millimeter of equal diameter length; a specific pull rate variation is shown in fig. 1;
(3) The constant diameter length is 800-1600mm, the furnace pressure is reduced from 200Torr to 165Torr, the pulling speed is reduced from 42mm/hr to 24mm/hr, the pulling speed change is shown in figure 1, and the furnace pressure change is shown in figure 2.
With the pull rate and furnace pressure processes of comparative examples 1 and 2 (FIGS. 1 and 2), dislocation appeared in the single crystal at the late stage of the isodiametric growth, and few portions having a resistivity of < 1.0mΩ. Cm were obtained after back cutting, which were approximately 40 to 50mm (as shown in FIG. 3).
Example 1
In the constant diameter process, the adopted process is specifically as follows:
(1) The equal diameter length is 0-100mm, and the furnace pressure is rapidly increased from 90Torr to 200Torr; the pulling speed is reduced from 55mm/hr to 45mm/hr; the change of the pulling speed is shown in fig. 1, and the change of the furnace pressure is shown in fig. 2;
(2) The constant diameter length is 100-800mm, and the furnace pressure is kept unchanged by 200Torr; the pulling speed is reduced from 45mm/hr to 42mm/hr, and the crystal pulling speed is reduced by 0-0.01mm/hr per millimeter of the isodiametric length; a specific pull rate variation is shown in fig. 1;
(3) The equivalent diameter length is 800-1600mm, the furnace pressure is reduced from 200Torr to 150Torr, the furnace pressure reduction rate is reduced by 0-0.1Torr per millimeter of the equivalent diameter length, and the specific furnace pressure change is shown in FIG. 2; the pulling speed is reduced from 42mm/hr to 20mm/hr, the specific change of the pulling speed is shown in figure 1, the pulling speed is reduced by 0.04mm/hr per millimeter of the equal diameter length and the pulling speed is reduced by 1400-1600mm at the equal diameter length of 800-1400 mm.
The single crystal obtained in this example is complete and dislocation-free, and can be obtained as a product with a resistivity of less than 1.0mΩ·cm and a length of 300-350 mm.
Therefore, the invention can ensure that dislocation is not generated in the later period of the equal diameter growth of the single crystal due to overlarge impurity concentration by perfect matching of pressure and pull speed, and can obtain the complete single crystal without dislocation.
Claims (1)
1. The preparation method of the heavily phosphorus-doped ultralow-resistance silicon single crystal is characterized in that the resistivity of the prepared silicon single crystal is less than 1m Ω & cm, and in the equal-diameter working procedure, the adopted process is as follows:
(1) In the early stage of the equal diameter, the pressure of the furnace chamber is increased from 70-90Torr to 180-220Torr, and the pressure of the furnace chamber is increased at a speed of 0.5-2Torr per millimeter of equal diameter length;
(2) In the middle of the equal diameter, the pressure of the furnace chamber is maintained to be unchanged at the high pressure which is increased to in the early period of the equal diameter;
(3) In the latter stage of the equal diameter, the pressure of the furnace chamber is reduced from the high pressure to 120-150Torr, and the pressure of the furnace chamber is reduced at a speed of 0.05-0.1Torr per millimeter of equal diameter length;
the isodiametric early stage is a stage with the isodiametric length of 0-100 mm; the mid-isodiametric period is a stage with the isodiametric length of 100-800 mm; the later isodiametric stage is a stage with the isodiametric length of 800-1600 mm;
in the whole isodiametric process, the crystal pulling speed is reduced at a speed of 0.01-0.2mm/hr per millimeter of isodiametric length, and the crystal pulling speed is reduced from 55-60mm/hr to 20-25mm/hr.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010184839A (en) * | 2009-02-12 | 2010-08-26 | Ｓｕｍｃｏ Ｔｅｃｈｘｉｖ株式会社 | Silicon single crystal and method of manufacturing the same |
| CN110730831A (en) * | 2017-04-25 | 2020-01-24 | 胜高股份有限公司 | Method for producing silicon single crystal, method for producing epitaxial silicon wafer, silicon single crystal, and epitaxial silicon wafer |
| CN110914483A (en) * | 2017-06-29 | 2020-03-24 | 胜高股份有限公司 | Method for producing silicon single crystal |
| CN113652737A (en) * | 2021-01-08 | 2021-11-16 | 隆基绿能科技股份有限公司 | Crystal pulling process method for monocrystalline silicon |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010184839A (en) * | 2009-02-12 | 2010-08-26 | Ｓｕｍｃｏ Ｔｅｃｈｘｉｖ株式会社 | Silicon single crystal and method of manufacturing the same |
| CN110730831A (en) * | 2017-04-25 | 2020-01-24 | 胜高股份有限公司 | Method for producing silicon single crystal, method for producing epitaxial silicon wafer, silicon single crystal, and epitaxial silicon wafer |
| CN110914483A (en) * | 2017-06-29 | 2020-03-24 | 胜高股份有限公司 | Method for producing silicon single crystal |
| CN113652737A (en) * | 2021-01-08 | 2021-11-16 | 隆基绿能科技股份有限公司 | Crystal pulling process method for monocrystalline silicon |
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